Evaluation of intermolecular interactions in thioxanthone derivatives: substituent effect on crystal diversity

A family of 9H-thioxanthen-9-one derivatives and two precursors, 2-[(4-bromophenyl) sulfanyl]-5-nitrobenzoic acid and 2-[(4-aminophenyl) sulfanyl]-5-nitrobenzoic acid, were synthesized and studied in order to assess the role of the different substituent groups in determining the supramolecular motifs. From our results we can conclude that Etter's rules are obeyed: whenever present the -COOH head to head strong hydrogen bonding dimer, R-2(2)(8) synthon, prevails as the dominant interaction. As for -NH2, the best donor when present also follows the expected hierarchy, an NH center dot center dot center dot O(COOH) was formed in the acid precursor (2) and an NH center dot center dot center dot O(C=O) in the thioxanthone (4). The main role played by weaker hydrogen bonds such as CH center dot center dot center dot O, and other intermolecular interactions, pi-pi and Br center dot center dot center dot O, as well as the geometric restraints of packing patterns shows the energetic interplay governing crystal packing. A common feature is the relation between the p-p stacking and the unit cell dimensions. A new synthon notation, R`, introduced in this paper, refers to the possibility of accounting for intra- and intermolecular interactions into recognizable and recurring aggregate patterns.

Comfort and functionality of pregnant women's feet study of kinetic parameters with silicon insoles

As gestantes, fruto das suas alterações fisiológicas e biomecânicas, constituem uma população de risco relativamente a dores ou lesões do sistema músculo-esquelético, nomeadamente, nos membros inferiores e coluna. Os objectivos deste estudo consistiram em avaliar: (i) a dor e o conforto dos pés durante a marcha: sem o uso de qualquer palmilha nas gestantes e no grupo de controlo; com a aplicação de uma palmilha de retropé e com a aplicação de uma palmilha completa (nas gestantes); (ii) a distribuição das pressões plantares e, (iii) as forças de reacção do solo nas mesmas condições experimentais. Avaliámos ainda a duração das diferentes fases do ciclo de marcha nas gestantes, com e sem palmilhas, e no grupo de controlo, sem o uso de palmilha. Os nossos resultados mostraram que: (i) as gestantes demoram mais tempo a completar a fase de apoio da marcha, (ii) têm um aumento significativo de dores nos pés, face ao grupo de controlo, (iii) as gestantes sentem menos dor e mais conforto quando realizam marcha, com palmilhas, especialmente com a palmilha completa, (iv) a palmilha completa redistribui as forças, diminui os valores de pressão e aumenta a área de contacto do pé com o solo. Os nossos resultados sugerem que, o uso da palmilha completa de silicone, durante a marcha, pode ser eficaz na melhoria da sintomatologia dolorosa e no aumento do conforto da grávida.

Membrane selectivity versus sensor response in hydrogenated amorphous silicon CHEMFETs using a semi-empirical model

Toxic amides, such as acrylamide, are potentially harmful to Human health, so there is great interest in the fabrication of compact and economical devices to measure their concentration in food products and effluents. The CHEmically Modified Field Effect Transistor (CHEMFET) based onamorphous silicon technology is a candidate for this type of application due to its low fabrication cost. In this article we have used a semi-empirical modelof the device to predict its performance in a solution of interfering ions. The actual semiconductor unit of the sensor was fabricated by the PECVD technique in the top gate configuration. The CHEMFET simulation was performed based on the experimental current voltage curves of the semiconductor unit and on an empirical model of the polymeric membrane. Results presented here are useful for selection and design of CHEMFET membranes and provide an idea of the limitations of the amorphous CHEMFET device. In addition to the economical advantage, the small size of this prototype means it is appropriate for in situ operation and integration in a sensor array.

Liquid crystal necklaces: cholesteric drops threaded by thin cellulose fibres

Liquid crystals in confined geometries exhibit numerous complex structures often including topological defects that are controlled by the nematic elasticity, chirality and surface anchoring. In this work, we study the structures of cholesteric droplets pierced by cellulose fibres with planar anchoring at droplet and fibre surfaces. By varying the temperature we demonstrate the role of twisting power and droplet diameter on the equilibrium structures. The observed structures are complemented by detailed numerical simulations of possible director fields decorated by defects. Three distinct structures, a bipolar and two ring configurations, are identified experimentally and numerically. Designing cholesteric liquid crystal microdroplets on thin long threads opens new routes to produce fibre waveguides decorated with complex microresonators.

Measurement of Photo Capacitance in Amorphous Silicon Photodiodes

This paper discusses the photodiode capacitance dependence on imposed light and applied voltage using different devices. The first device is a double amorphous silicon pin-pin photodiode; the second one a crystalline pin diode and the last one a single pin amorphous silicon diode. Double amorphous silicon diodes can be used as (de)multiplexer devices for optical communications. For short range applications, using plastic optical fibres, the WDM (wavelength-division multiplexing) technique can be used in the visible light range to encode multiple signals. Experimental results consist on measurements of the photodiode capacitance under different conditions of imposed light and applied voltage. The relation between the capacitive effects of the double diode and the quality of the semiconductor internal junction will be analysed. The dynamics of charge accumulations will be measured when the photodiode is illuminated by a pulsed monochromatic light.

A cellulose liquid crystal motor: a steam engine of the second kind

The salient feature of liquid crystal elastomers and networks is strong coupling between orientational order and mechanical strain. Orientational order can be changed by a wide variety of stimuli, including the presence of moisture. Changes in the orientation of constituents give rise to stresses and strains, which result in changes in sample shape. We have utilized this effect to build soft cellulose-based motor driven by humidity. The motor consists of a circular loop of cellulose film, which passes over two wheels. When humid air is present near one of the wheels on one side of the film, with drier air elsewhere, rotation of the wheels results. As the wheels rotate, the humid film dries. The motor runs so long as the difference in humidity is maintained. Our cellulose liquid crystal motor thus extracts mechanical work from a difference in humidity.

Light shutters from nanocrystalline cellulose rods in a nematic liquid crystal

This work reports a recently developed electro-optical (EO) device that can potentially be used as a light shutter or a privacy window. By using nanocrystalline cellulose rods, we were able to improve some of the most relevant parameters characterising the EO behaviour. A brief description of the proposed working mechanism for these devices is presented, and numerical simulations based on this mechanism of both the optical transmission and the cells' electrical capacitance are compared with the obtained results, validating the underlying working model considered.

Water-Based Cellulose Liquid Crystal System Investigated by Rheo-NMR

Water-based cellulose cholesteric liquid crystalline phases at rest can undergo structural changes induced by shear flow. This reflects on the deuterium spectra recorded when the system is investigated by rheo-nuclear magnetic resonance (rheo-NMR) techniques. In this work, the model system hydroxypropylcellulose (HPC)+water is revisited using rheo-NMR to clarify unsettled points regarding its behavior under shear and in relaxation. The NMR spectra allow the identification of five different stable ordering states, within shear and relaxation, which are well integrated in a mesoscopic picture of the system's structural evolution under shear and relaxation. This picture emerging from the large body of studies available for this system by other experimental techniques, accounts well for the NMR data and is in good agreement with the three distinct regions of steady shear flow recognized for some lyotropic LC polymers. Shear rates in between 0.1 and 1.0 s(-1) where investigated using a Taylor-Couette flow and deuterated water was used as solvent for the deuterium NMR (DNMR) analysis.

Sub-micron structuring of silicon using femtosecond laser interferometry

We report the fabrication of planar sub-micron gratings in silicon with a period of 720 nm using a modified Michelson interferometer and femtosecond laser radiation. The gratings consist of alternated stripes of laser ablated and unmodified material. Ablated stripes are bordered by parallel ridges which protrude above the unmodified material. In the regions where ridges are formed, the laser radiation intensity is not sufficient to cause ablation. Nevertheless, melting and a significant temperature increase are expected, and ridges may be formed due to expansion of silicon during resolidification or silicon oxidation. These conclusions are consistent with the evolution of the stripes morphology as a function of the distance from the center of the grating. (C) 2013 Elsevier Ltd. All rights reserved.

Simulation and theory of hybrid aligned liquid crystal films

We present a study of the effects of nanoconfinement on a system of hard Gaussian overlap particles interacting with planar substrates through the hard-needle-wall potential, extending earlier work by two of us [D. J. Cleaver and P. I. C. Teixeira, Chem. Phys. Lett. 338, 1 (2001)]. Here, we consider the case of hybrid films, where one of the substrates induces strongly homeotropic anchoring, while the other favors either weakly homeotropic or planar anchoring. These systems are investigated using both Monte Carlo simulation and density-functional theory, the latter implemented at the level of Onsager's second-virial approximation with Parsons-Lee rescaling. The orientational structure is found to change either continuously or discontinuously depending on substrate separation, in agreement with earlier predictions by others. The theory is seen to perform well in spite of its simplicity, predicting the positional and orientational structure seen in simulations even for small particle elongations.

Shear-induced lamellar phase of an ionic liquid crystal at room temperature

The phase behaviour of a number of N-alkylimidazolium salts was studied using polarizing optical microscopy, differential scanning calorimetry and X-ray diffraction. Two of these compounds exhibit lamellar mesophases at temperatures above 50 degrees C. In these systems, the liquid crystalline behaviour may be induced at room temperature by shear. Sheared films of these materials, observed between crossed polarisers, have a morphology that is typical of (wet) liquid foams: they partition into dark domains separated by brighter (birefringent) walls, which are approximately arcs of circle and meet at "Plateau borders" with three or more sides. Where walls meet three at a time, they do so at approximately 120 degrees angles. These patterns coarsen with time and both T1 and T2 processes have been observed, as in foams. The time evolution of domains is also consistent with von Neumann's law. We conjecture that the bright walls are regions of high concentration of defects produced by shear, and that the system is dominated by the interfacial tension between these walls and the uniform domains. The control of self-organised monodomains, as observed in these systems, is expected to play an important role in potential applications.

How foam-like is the shear-induced lamellar phase of an ionic liquid crystal?

Philosophical Magazine Letters Volume 88, Issue 9-10, 2008 Special Issue: Solid and Liquid Foams. In commemoration of Manuel Amaral Fortes

The 27th British liquid crystal society annual meeting 2013, Cambridge

Attending the British Liquid Crystal Society’s (BLCS) Annual Meeting was a formative experience in my days as a PhD student, starting way back in the 1990s. At that time, this involved travelling to (to me) exotic parts of the United Kingdom, such as Reading, Oxford or Manchester, away from Southampton where I was based. Some postdoctoral years in a different country followed, and three BLCS Meetings were missed, until in 1997 and 1998, I was able to attend again, in Southampton and Leeds, respectively. Not much had changed from my student days, the size and the format were still about the same, many of the leading characters were still around, and the closing talk would still be given by John Lydon. Well, at some point, I got myself a proper academic job on the Continent and stopped attending BLCS Annual Meetings altogether. The fond memories of my youth started to fade. Were the Meetings still on? It seemed so, as old friends and acquaintances would occasionally recount attending them, and even winning prizes at them. But, it all seemed rather remote now. Until, that is, it came to pass that the 27th BLCS Meeting would be held in Selwyn College, Cambridge, just down (or up, depending on how you look at it) the road from the Isaac Newton Institute, where I was spending part of my sabbatical leave. The opportunity to resume attendance could not be missed. A brief e-mail exchange with the organisers, and a cheque to cover the fee, duly secured this. And thus, it was with trepidation that I approached my first BLCS Annual Meeting in more than a decade.

Lightweight amorphous silicon photovoltaic modules on flexible plastic substrate

Solar cells on lightweight and flexible substrates have advantages over glass-or wafer-based photovoltaic devices in both terrestrial and space applications. Here, we report on development of amorphous silicon thin film photovoltaic modules fabricated at maximum deposition temperature of 150 degrees C on 100 mu m thick polyethylene-naphtalate plastic films. Each module of 10 cm x 10 cm area consists of 72 a-Si:H n-i-p rectangular structures with transparent conducting oxide top electrodes with Al fingers and metal back electrodes deposited through the shadow masks. Individual structures are connected in series forming eight rows with connection ports provided for external blocking diodes. The design optimization and device performance analysis are performed using a developed SPICE model.

Liquid crystal beads constrained on thin cellulosic fibers: Electric field induced microrotors and N-I transition

We directly visualize the response of nematic liquid crystal drops of toroidal topology threaded in cellulosic fibers, suspended in air, to an AC electric field and at different temperatures over the N-I transition. This new liquid crystal system can exhibit non-trivial point defects, which can be energetically unstable against expanding into ring defects depending on the fiber constraining geometries. The director anchoring tangentially near the fiber surface and homeotropically at the air interface makes a hybrid shell distribution that in turn causes a ring disclination line around the main axis of the fiber at the center of the droplet. Upon application of an electric field, E, the disclination ring first expands and moves along the fiber main axis, followed by the appearance of a stable "spherical particle" object orbiting around the fiber at the center of the liquid crystal drop. The rotation speed of this particle was found to vary linearly with the applied voltage. This constrained liquid crystal geometry seems to meet the essential requirements in which soliton-like deformations can develop and exhibit stable orbiting in three dimensions upon application of an external electric field. On changing the temperature the system remains stable and allows the study of the defect evolution near the nematic-isotropic transition, showing qualitatively different behaviour on cooling and heating processes. The necklaces of such liquid crystal drops constitute excellent systems for the study of topological defects and their evolution and open new perspectives for application in microelectronics and photonics.